JP5882990B2 - Modified pigment - Google Patents

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority to US Provisional Patent Application No. 61 / 395,649, filed May 14, 2010, based on Section 119 of the U.S. Patent Act. Is incorporated herein by reference.

  The present disclosure relates to pigments modified with organic groups containing 5-membered aromatic heterocycles, and related compositions, articles, and methods.

  The ink composition usually contains a water-soluble dye or pigment. While some inks based on dyes are suitable for their intended purpose, there are some disadvantages when using dyes as ink jet ink compositions. For example, water-soluble dyes can dissolve and flow when exposed to moisture or water. If the dye image comes into contact with the felt-tip pen marker, or is rubbed or touched with a finger, it becomes even more dirty or rubbed off. Dyes also have low light resistance when exposed to visible light, ultraviolet light, or sunlight. A pigment can also be used as a colorant in the ink composition.

  The inventors have found that certain diazonium salts containing a 5-membered aromatic heterocycle exhibit high activity upon modification of the pigment, thereby resulting in a modified pigment having a high processing level and high dispersibility in the ink composition. I realized that. If such a diazonium salt is used, it may be possible to effectively modify pigments that may not be modified by other methods.

  In one aspect, the present disclosure provides (1) reacting a diazotizing agent with a primary amine containing a 5-membered aromatic heterocycle and an amino group directly bonded to the 5-membered aromatic heterocycle, thereby producing a 5-membered aromatic Forming a reaction mixture containing a diazonium salt containing a group heterocycle, and (2) after forming the diazonium salt, a pigment is added to the reaction mixture, thereby forming a modified pigment containing a 5-membered aromatic heterocycle And a method including the steps. A 5-membered aromatic heterocycle contains at least two endocyclic heteroatoms, at least one of which is a nitrogen atom.

  In another aspect, the present disclosure reacts a pigment with a diazonium salt containing a 5-membered aromatic heterocycle and a diazonium group bonded directly to the 5-membered aromatic heterocycle, thereby containing the 5-membered aromatic heterocycle Characterized in that it comprises forming a modified pigment. A 5-membered aromatic heterocycle contains three endocyclic heteroatoms, at least two of which are nitrogen atoms.

の陽イオンを含む。
この式において、ＸはＯ、Ｎ（Ｒ_a）、またはＳであり；かつＲ₁およびＲ₂はそれぞれ独立して、Ｈ、Ｃ₁−Ｃ₁₀アルキル、Ｃ₂−Ｃ₁₀アルケニル、Ｃ₂−Ｃ₁₀アルキニル、Ｃ₃−Ｃ₂₀シクロアルキル、Ｃ₃−Ｃ₂₀シクロアルケニル、Ｃ₁−Ｃ₂₀ヘテロシクロアルキル、Ｃ₁−Ｃ₂₀ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ_b、ＣＯＯＲ_b、ＯＣ（Ｏ）Ｒ_b、Ｃ（Ｏ）Ｒ_b、Ｃ（Ｏ）ＮＲ_bＲ_c、ＳＯ₃Ｒ_c、ＮＲ_bＲ_c、またはＮ⁺（Ｒ_bＲ_cＲ_d）Ｙであり、
Ｒ_a、Ｒ_b、Ｒ_c、およびＲ_dがそれぞれ独立して、Ｈ、Ｃ₁−Ｃ₁₀アルキル、Ｃ₃−Ｃ₂₀シクロアルキル、Ｃ₁−Ｃ₂₀ヘテロシクロアルキル、アリール、またはヘテロアリールであり、Ｙが陰イオンである。ただし、Ｒ₁およびＲ₂の少なくとも１つがＨではないことを条件とする。 In another aspect, the disclosure features a method that includes reacting a pigment with a diazonium salt containing a 5-membered aromatic heterocycle, thereby forming a modified pigment containing the 5-membered aromatic heterocycle. The diazonium salt has the formula (IIa):

Of cations.
In this formula, X is O, N (R _a ), or S; and R ₁ and R ₂ are each independently H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C _2- C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl, C ₁ -C ₂₀ heterocycloalkyl, C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, cyano, OR _b, COOR _b , OC (O) R _b , C (O) R _b , C (O) NR _b R _c , SO ₃ R _c , NR _b R _c , or N ⁺ (R _b R _c R _d ) Y ,
R _a , R _b , R _c , and R _d are each independently H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, or heteroaryl Y is an anion. Provided that at least one of R ₁ and R ₂ is not H.

  In another aspect, the disclosure features an ink composition that includes a liquid vehicle and a material that includes a pigment and an organic group attached to the pigment. The organic group contains only one aromatic ring, and the only aromatic ring is a 5-membered aromatic heterocycle. A 5-membered aromatic heterocycle contains three endocyclic heteroatoms, at least two of which are nitrogen atoms.

  In another aspect, the disclosure features a composition that includes a pigment and an organic group attached to the pigment. The organic group contains only one aromatic ring, and the only aromatic ring is a 5-membered aromatic heterocycle. A 5-membered aromatic heterocycle contains three endocyclic heteroatoms, at least two of which are nitrogen atoms.

で表わされる。
この式において、ＸはＯ、Ｎ（Ｒ_a）、またはＳであり；かつＲ₁およびＲ₂は、それぞれ独立してＨ、Ｃ₁−Ｃ₁₀アルキル、Ｃ₂−Ｃ₁₀アルケニル、Ｃ₂−Ｃ₁₀アルキニル、Ｃ₃−Ｃ₂₀シクロアルキル、Ｃ₃−Ｃ₂₀シクロアルケニル、Ｃ₁−Ｃ₂₀ヘテロシクロアルキル、Ｃ₁−Ｃ₂₀ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ_b、ＣＯＯＲ_b、ＯＣ（Ｏ）Ｒ_b、Ｃ（Ｏ）Ｒ_b、Ｃ（Ｏ）ＮＲ_bＲ_c、ＳＯ₃Ｒ_c、ＮＲ_bＲ_c、またはＮ⁺（Ｒ_bＲ_cＲ_d）Ｙであり、
Ｒ_a、Ｒ_b、Ｒ_c、およびＲ_dは、それぞれ独立してＨ、Ｃ₁−Ｃ₁₀アルキル、Ｃ₃−Ｃ₂₀シクロアルキル、Ｃ₁−Ｃ₂₀ヘテロシクロアルキル、アリール、またはヘテロアリールであり、かつＹは陰イオンである。ただし、Ｒ₁およびＲ₂のうち少なくとも１つはＨではないことを条件とする。 In another aspect, the disclosure features an ink composition that includes a liquid vehicle and a material that includes a pigment and an organic group attached to the pigment. The organic group has the formula (IIb):

It is represented by
In this formula, X is O, N (R _a ), or S; and R ₁ and R ₂ are each independently H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C _2- C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl, C ₁ -C ₂₀ heterocycloalkyl, C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, cyano, OR _b, COOR _b , OC (O) R _b , C (O) R _b , C (O) NR _b R _c , SO ₃ R _c , NR _b R _c , or N ⁺ (R _b R _c R _d ) Y ,
R _a , R _b , R _c , and R _d are each independently H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, or heteroaryl. And Y is an anion. Provided that at least one of R ₁ and R ₂ is not H.

  In another aspect, the disclosure features a composition that includes a pigment and an organic group attached to the pigment. The organic group is represented by the above formula (IIb).

  In another aspect, the disclosure features an ink composition that includes a liquid vehicle and a material that includes a pigment and an organic group attached to the pigment. The organic group comprises a 5-membered aromatic heterocycle containing 4 ring heteroatoms, at least 3 of which are nitrogen atoms.

  In another aspect, the disclosure features a composition that includes a pigment and an organic group attached to the pigment. The organic group comprises a 5-membered aromatic heterocycle containing 4 ring heteroatoms, at least 3 of which are nitrogen atoms.

  Other features, objects, and advantages of the disclosure will be apparent from the description and the claims.

  In the present disclosure, generally, a primary amine containing a 5-membered aromatic heterocycle is reacted with a diazotizing agent to form a diazonium salt, which is further processed into a pigment to be dispersed in an ink composition. The present invention relates to a method capable of forming a modified pigment having improved properties.

  Primary amines generally contain a 5-membered aromatic heterocycle and an amino group. In some embodiments, the 5-membered aromatic heterocycle is the only aromatic ring in the primary amine. In other embodiments, the primary amine contains one or more additional aromatic rings (eg, aromatic heterocycles, or aromatic rings that do not contain aromatic heterocycle atoms). One or more additional aromatic rings may be covalently bonded or fused to a 5-membered aromatic heterocycle. In certain embodiments, the primary amine may contain one or more amino groups (eg, 2 or 3 amino groups).

  Usually, the amino group is directly bonded to the 5-membered aromatic heterocycle. Although not intending to be bound by theory, a diazonium salt derived from a primary amine in which an amino group is directly bonded to a 5-membered aromatic heterocyclic ring does not have the amino group directly bonded to the 5-membered aromatic heterocyclic ring. Compared to those derived from primary amines, it is believed to exhibit higher activity in modifying pigments. In addition, although not intending to be bound by theory, a diazonium salt derived from a primary amine in which an amino group is directly bonded to a 5-membered aromatic heterocyclic ring has an aromatic group other than the 5-membered aromatic heterocyclic ring. It is believed to be more active in modifying pigments than those derived from primary amines that are directly bonded to a ring (eg, a 6-membered aromatic ring or aromatic heterocycle).

  In general, a 5-membered aromatic heterocycle in a primary amine contains at least two endocyclic heteroatoms (eg, 2, 3, or 4 endocyclic heteroatoms).

  When the 5-membered aromatic heterocycle in the primary amine contains three endocyclic heteroatoms, at least two of the endocyclic heteroatoms can be nitrogen atoms. Examples of such 5-membered aromatic heterocycles include 1,2,4-triazolyl, 1,2,3-triazolyl, 1,3,4-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,3- Examples include thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-oxadiazolyl, and 1,2,5-oxadiazolyl.

の化合物であり得る。
この式において、ＸはＯ、Ｎ（Ｒ_a）、またはＳであり得、かつＲ₁はＨ、Ｃ₁−Ｃ₁₀アルキル、Ｃ₂−Ｃ₁₀アルケニル、Ｃ₂−Ｃ₁₀アルキニル、Ｃ₃−Ｃ₂₀シクロアルキル、Ｃ₃−Ｃ₂₀シクロアルケニル、Ｃ₁−Ｃ₂₀ヘテロシクロアルキル、Ｃ₁−Ｃ₂₀ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ_b、ＣＯＯＲ_b、ＯＣ（Ｏ）Ｒ_b、Ｃ（Ｏ）Ｒ_b、Ｃ（Ｏ）ＮＲ_bＲ_c、ＳＯ₃Ｒ_c、ＮＲ_bＲ_c、またはＮ⁺（Ｒ_bＲ_cＲ_d）Ｙであり得、ここで、Ｒ_a、Ｒ_b、Ｒ_c、Ｒ_dは、それぞれ独立して、Ｈ、Ｃ₁−Ｃ₁₀アルキル、Ｃ₃−Ｃ₂₀シクロアルキル、Ｃ₁−Ｃ₂₀ヘテロシクロアルキル、アリール、またはヘテロアリールであり得、かつＹは陰イオンであり得る。一般に、Ｙは任意の好適な陰イオン、例えば塩化物、臭化物、ヨウ化物、硫酸塩、硝酸塩、リン酸塩、クエン酸塩、メタンスルホン酸塩、トリフルオロ酢酸塩、酢酸塩、リンゴ酸塩、トシレート、酒石酸塩、フマル酸塩、グルタミン酸塩、グルクロン酸塩、乳酸塩、グルタル酸塩、またはマレイン酸塩であり得る。 When the 5-membered aromatic heterocycle in the primary amine contains 3 heteroatoms, the primary amine is of formula (I):

The compound may be
In this formula, X can be O, N (R _a ), or S, and R ₁ is H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, C _3- C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl, C ₁ -C ₂₀ heterocycloalkyl, C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, cyano, OR _b , COOR _b , OC (O) R _b , C (O) R _b , C (O) NR _b R _c , SO ₃ R _c , NR _b R _c , or N ⁺ (R _b R _c R _d ) Y, where R _a , R _b , R _c , R _d can each independently be H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, or heteroaryl. Y can be an anion. In general, Y is any suitable anion such as chloride, bromide, iodide, sulfate, nitrate, phosphate, citrate, methanesulfonate, trifluoroacetate, acetate, malate, It can be tosylate, tartrate, fumarate, glutamate, glucuronate, lactate, glutarate, or maleate.

Subsets of compounds of formula (I) are optionally substituted with R ₁ being H, C ₁ -C ₁₀ alkyl, COOR _a , C (O) NH (C ₁ -C ₁₀ alkyl), or C ₁ -C ₁₀ alkyl Wherein C ₁ -C ₁₀ alkyl is optionally substituted with fluoro, OR _a COOR _a , or N ⁺ (R _b R _c R _d ). For example, the primary amine of formula (I) can be compounds 1-10 listed below.

As used herein, the term “alkyl” refers to a saturated straight or branched acyclic hydrocarbon moiety, such as —CH ₃ or —CH (CH ₃ ) ₂ , for example. The term “alkenyl” refers to a straight or branched acyclic hydrocarbon moiety containing at least one double bond, eg, —CH═CH—CH ₃ . The term “alkynyl” refers to a straight or branched acyclic hydrocarbon moiety containing at least one triple bond, eg, —C≡C—CH ₃ . The term “cycloalkyl” refers to a saturated cyclic hydrocarbon moiety such as, for example, cyclohexyl. The term “cycloalkenyl” refers to a non-aromatic cyclic hydrocarbon moiety containing at least one double bond, such as, for example, cyclohexenyl. The term “heterocycloalkyl” refers to a saturated cyclic moiety having at least one endocyclic heteroatom (eg, N, O, or S), such as 4-tetrahydropyranyl. The term “heterocycloalkenyl” refers to a non-aromatic cyclic moiety having at least one endocyclic heteroatom (eg, N, O, or S) and at least one endocyclic double bond, such as, for example, pyranyl. The term “aryl” refers to a hydrocarbon moiety having one or more aromatic rings. Examples of aryl moieties include phenyl (Ph), phenylene, naphthyl, naphthylene, pyrenyl, anthryl, and phenanthryl. The term “heteroaryl” refers to a moiety containing at least one heteroatom (eg, N, O, or S) and having one or more aromatic rings. Examples of heteroaryl moieties include furyl, furylene, fluorenyl, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinazolinyl, quinolyl, isoquinolyl, and indolyl.

As described herein, alkyl, alkynyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, and heteroaryl include both substituted and unsubstituted moieties unless otherwise stated. . Substituents for cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, and heteroaryl include C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl, C ₁ -C ₂₀ heterocycloalkyl, C ₁ -C ₂₀ heterocycloalkenyl, C ₁ -C ₁₀ alkoxy, aryl, aryloxy, heteroaryl, heteroaryl aryloxy, amino, C ₁ -C ₁₀ alkylamino, C ₁ -C ₂₀ dialkylamino, arylamino, diarylamino, C ₁ -C ₁₀ alkyl sulfonic amino, arylsulfonic amino, C ₁ -C ₁₀ alkylimino, arylimino , C ₁ -C ₁₀ alkyl sulfonic imino, arylsulfonic Lee Bruno, hydroxyl, halo, thio, C ₁ -C ₁₀ alkylthio, arylthio, C ₁ -C ₁₀ alkylsulfonyl, arylsulfonyl, acylamino, aminoacyl, Aminothioacyl, amidino, guanidine, ureido, cyano, nitro, nitroso, azide, Examples include, but are not limited to acyl, thioacyl, acyloxy, carboxyl, and carboxylate. On the other hand, alkyl, alkenyl, or as may become substituents for alkynyl, except C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, and C ₂ -C ₁₀ alkynyl, like all the above substituents It is done. Cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, and heteroaryl also include those containing fused rings.

  When the 5-membered aromatic heterocycle in the primary amine contains two endocyclic heteroatoms, at least one of the endocyclic heteroatoms can be a nitrogen atom. Examples of such 5-membered aromatic heterocycles include imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, and isoxazolyl.

の化合物であり得る。この式において、ＸはＯ、Ｎ（Ｒ_a）、またはＳであり得、かつＲ₁およびＲ₂がそれぞれ独立してＨ、Ｃ₁−Ｃ₁₀アルキル、Ｃ₂−Ｃ₁₀アルケニル、Ｃ₂−Ｃ₁₀アルキニル、Ｃ₃−Ｃ₂₀シクロアルキル、Ｃ₃−Ｃ₂₀シクロアルケニル、Ｃ₁−Ｃ₂₀ヘテロシクロアルキル、Ｃ₁−Ｃ₂₀ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ_b、ＣＯＯＲ_b、ＯＣ（Ｏ）Ｒ_b、Ｃ（Ｏ）Ｒ_b、Ｃ（Ｏ）ＮＲ_bＲ_c、ＳＯ₃Ｒ_c、ＮＲ_bＲ_c、またはＮ⁺（Ｒ_bＲ_cＲ_d）Ｙであり得、ここで、Ｒ_a、Ｒ_b、Ｒ_c、およびＲ_dはそれぞれ独立してＨ、Ｃ₁−Ｃ₁₀アルキル、Ｃ₃−Ｃ₂₀シクロアルキル、Ｃ₁−Ｃ₂₀ヘテロシクロアルキル、アリール、またはヘテロアリールであり得、かつＹは陰イオン（例えば上述したようなもの）であり得る。式（ＩＩ）の化合物のサブセットは、その中のＲ₁およびＲ₂がそれぞれ独立してＨ、シアノ、ＣＯＯＲ_a、またはＳＯ₃Ｒ_aであるものであり得る。例えば、式（ＩＩ）の１級アミンは、

When the 5-membered aromatic heterocycle in the primary amine contains two endocyclic heteroatoms, the primary amine is of formula (II)

The compound may be In this formula, X can be O, N (R _a ), or S, and R ₁ and R ₂ are each independently H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C _2- C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl, C ₁ -C ₂₀ heterocycloalkyl, C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, cyano, OR _b, COOR _b , OC (O) R _b , C (O) R _b , C (O) NR _b R _c , SO ₃ R _c , NR _b R _c , or N ⁺ (R _b R _c R _d ) Y Where R _a , R _b , R _c , and R _d are each independently H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, Or can be heteroaryl and Y is an anion (eg as described above) It can be in. A subset of compounds of formula (II) may be those in which R ₁ and R ₂ are each independently H, cyano, COOR _a , or SO ₃ R _a . For example, the primary amine of formula (II) is

When the 5-membered aromatic heterocycle in the primary amine contains 4 ring heteroatoms, at least 3 of the ring heteroatoms may be nitrogen atoms. An example of such a 5-membered aromatic heterocycle is tetrazolyl. An example of a primary amine containing tetrazolyl is

The primary amines described herein can also contain one or two ionic groups. An ionic group is a group (eg, an anionic group or a cationic group) that can form an ionic group in the medium used. An ionic group that forms an anion includes, for example, an acidic group or a salt thereof. Examples of such ionic groups include COOH, SO ₃ H, and salts thereof. Examples of ionic groups that form cations include amino groups and salts thereof. Other suitable ionic groups are described, for example, in US Pat. No. 5,992,118. Without wishing to be bound by theory, pigments modified with diazonium salts derived from primary amines containing ionic groups become modified pigments containing ionic groups and are utilized in media (eg, inkjet inks). It is considered that the dispersibility in the aqueous medium) in the ink composition is improved. Ionic groups, either attached directly to the 5-membered heteroaromatic ring in a primary amine, or (may be optionally substituted by a substituent as described herein) C ₁ -C ₁₀ alkyl group or an aryl group such as To a 5-membered aromatic heterocyclic ring.

  The primary amines described herein can be purchased from commercial sources or made by methods known in the art.

In general, a primary amine containing a 5-membered aromatic heterocycle and an amino group reacts with a diazotizing agent to form a diazonium salt containing a 5-membered aromatic heterocycle and a diazonium group (ie, —N ₂ ⁺ ). Can do. During this reaction, the amino group in the primary amine is usually converted to a diazonium group, but the 5-membered aromatic heterocycle often remains unchanged. Suitable diazotizing agents that can be used in this reaction include nitrous acid or salts thereof (for example, salts containing alkali metals or alkaline earth metals), nitrosyl groups, sulfuric acid, dinitrogen trioxide, alkyl nitrites, There are nitrosyl chloride and nitrosyl bromide. The diazotizing agent can be made in advance or in situ (eg, by adding sodium nitride and acid to a mixture containing a primary amine).

Scheme 1 below shows a representative method for synthesizing diazonium salts using primary amines of formula (I) and formula (II). In this scheme, X, R ₁ , and R ₂ can be the same as defined above.

を含むジアゾニウム塩を形成し得る。 As shown in Scheme 1, primary amines of formula (I) and (II) are reacted with a diazotizing agent (eg, HNO ₂ ) to form diazonium salts containing cations of formula (Ia) and (IIa), respectively. Can be formed. For example, the above compounds 1 to 3 and 11 to 14 are respectively the following cations:

A diazonium salt containing can be formed.

  The reaction shown in Scheme 1 is usually carried out in the presence of an acid such as sulfuric acid, phosphoric acid, acetic acid, or propionic acid, or a mixture thereof. Preferably, such reactions are conducted at a pH of at most about 2.5 (eg, at most about 2, at most about 1.5, or at most about 1). If the primary amine contains an acidic group (eg, an acidic group of carboxylic acid or sulfuric acid), the additional amount of acid required to form the diazonium group can be reduced or even stopped.

  The diazonium salt formed above reacts with the pigment in the liquid medium to add at least one organic group (eg, an organic group containing a 5-membered aromatic heterocycle) to the surface of the pigment, thereby forming an ink composition. A modified pigment having improved dispersibility in the product can be formed.

  In general, the pigment can be any pigment that can be modified by the attachment of at least one organic group. Suitable pigments include carbon black and colored pigments that do not contain primary amines other than carbon. The colored pigment can be blue, brown, cyan, green, purple, magenta, red, or yellow, as well as mixtures thereof. Suitable types of colored pigments include, for example, anthraquinone, phthalocyanine blue, phthalocyanine green, diazo, monoazo, pyranthrone, perylene, heterocyclic yellow, quinacridone, and (thio) indigoid . Examples of phthalocyanine blue are copper phthalocyanine blue and its derivatives (blue pigment 15). Examples of quinacridone series include orange pigment 48, orange pigment 49, red pigment 122, red pigment 192, red pigment 202, red pigment 206, red pigment 207, red pigment 209, purple pigment 19, and purple pigment 42. Can be mentioned. Examples of anthraquinone series include red pigment 43, red pigment 194 (perinone red), red pigment 216 (brominated pyranthrone red), and red pigment 226 (pyrantron red). Examples of perylene systems include red pigment 123 (Vermilion), red pigment 149 (Scarlet), red pigment 179 (maroon), red pigment 190 (red), purple pigment, red pigment 189 (yellowish red), And red pigment 224.

  Examples of the thioindigoid type include red pigment 86, red pigment 87, red pigment 88, red pigment 181, red pigment 198, purple pigment 36, and purple pigment 38.

  Examples of heterocyclic yellow include yellow pigment 117 and yellow pigment 138. Examples of other suitable pigments include yellow pigments 1, 74, 155, 180, 185, 213, 218, 220, and 221, red pigments 254 and 269, and blue pigments 16 and 60. Examples of other suitable colored pigments are described in Color Index, 3rd edition (The Society of Dyers and Cikiyrusts, 1982).

  While not intending to be bound by theory, the diazonium salts described herein are high in processing levels by exhibiting high activity in modifying pigments, and thus in ink compositions (eg, aqueous compositions). It is believed to produce modified pigments with improved dispersibility. In addition, while not intending to be bound by theory, it is believed that the use of the diazonium salts described herein can effectively modify pigments that cannot be modified with conventional diazonium salts. For example, compounds 1, 3, and 11 can be used to effectively modify yellow pigment 74 that cannot be modified with any other known diazonium salt as far as the inventor is aware.

  A suitable liquid medium for the pigment modification reaction may be a polar medium. Examples of suitable media include water, media containing water, or media containing alcohol (eg, ethanol or isopropanol). The liquid medium can be a solution, dispersion, slurry, or emulsion.

  The diazonium salt can be prepared in situ, ie in the presence of the pigment to be modified. For example, a modified pigment can be prepared by first adding a primary amine, acid, and pigment to a liquid medium (eg, water) to form a mixture, and then adding a diazotizing agent to the mixture. With this method, since the diazonium salt can react with the pigment as soon as it is formed, the decomposition of the diazonium salt can be reduced.

  Alternatively, the diazonium salt can be pre-formed, i.e. formed in the mixture before adding the pigment to be modified. For example, first a primary amine, an acid, and a diazotizing agent (eg, sodium nitrite) are added to a liquid medium (eg, water) to form a diazonium salt and then the mixture thus formed. A pigment is added to prepare a modified pigment. Since primary amines containing a 5-membered aromatic heterocycle are usually low in basicity, a large amount of acid is required to form a diazonium salt. By preparing the diazonium salt in advance, the excess amount of acid used in such a reaction can be minimized. On the other hand, when the diazonium salt is formed in situ, the amount of liquid medium required for such a reaction is greater than when the diazonium salt is formed in advance, so that more acid is required to form the diazonium salt. Although required, it can be more difficult to remove this acid during the process of isolating the modified pigment. Thus, compared to the method of preparing the diazonium salt in situ, the pre-formation of the diazonium salt can reduce manufacturing costs.

  The diazonium salt only needs to be stable to the extent that it can react with the pigment to be modified. For example, a pigment modification reaction can be carried out using a diazonium salt which is considered unstable and easily decomposed. Furthermore, the modification reaction of the pigment can be carried out at a high temperature at which the diazonium salt is likely to be decomposed. Although the diazonium salt is somewhat lost due to decomposition when the temperature is increased, it can be advantageous to carry out the modification reaction of the pigment at a high temperature, increasing the solubility of the diazonium salt in the reaction medium or its reactivity to the pigment. . Preferably, the modified pigment does not contain by-products or unbound compounds.

の有機基が表面に結合した変性顔料を形成する。式（Ｉｂ）および（ＩＩｂ）において、Ｘ、Ｒ₁、およびＲ₂は、式（Ｉ）および（ＩＩ）に関して定義されたものと同じであり得る。一例として、上記の化合物１〜３、および１１〜１４に由来するジアゾニウムで変性された顔料では、次の有機基

が表面に結合している。ジアゾニウム塩中のジアゾニウム基の反応性または安定性によって、式（Ｉｂ）および（ＩＩｂ）の有機基は、顔料の表面に直接かまたはジアゾ基（即ち、−Ｎ＝Ｎ−）を通じて結合し得る。 In a modified pigment prepared from a diazonium salt containing a 5-membered aromatic heterocycle, the 5-membered aromatic heterocycle is bonded to the surface. For example, diazonium salts containing cations of formula (Ia) and formula (IIa) react with pigments to give formulas (Ib) and (IIb) respectively.

To form a modified pigment having organic groups bonded to the surface. In formulas (Ib) and (IIb), X, R ₁ , and R ₂ can be the same as defined for formulas (I) and (II). As an example, in the pigment modified with diazonium derived from the above compounds 1 to 3 and 11 to 14, the following organic group

Is bound to the surface. Depending on the reactivity or stability of the diazonium group in the diazonium salt, the organic groups of formulas (Ib) and (IIb) can be bound to the pigment surface either directly or through a diazo group (ie, —N═N—).

5-membered aromatic heterocycle, based on nitrogen surface area of the modified pigment may be present in from about 2.7 mmol / cm ² ~ about 66.6 mmol / cm ² treatment level on the surface of the modified pigment. The term “treatment level” as used herein refers to the amount of organic groups per unit of the surface of the modified pigment. The nitrogen surface area used for the determination of the treatment level described above can be obtained by using ASTM D-4820. When an organic group containing an ionic group (for example, a carboxylic acid group) is introduced on the surface of the pigment, the treatment level of the organic group can be determined by measuring the amount of counter ion relative to the ionic group. it can. For example, when the counter ion is a sodium ion, the amount of sodium ion can be measured using an ion selective electrode, atomic absorption spectroscopy, or inductively coupled plasma.

If the modified pigment includes carbon black, based on nitrogen surface area of the modified pigment, the processing level is in the range of from about 2.7 mmol / cm ² ~ about 53 mmol / cm ² (e.g., about 6.7 mmol / cm ² ˜about 32 mmol / cm ² ). If the modified pigment include coloring pigment other than carbon black, the processing level is in the range of from about 3.3 mmol / cm ² ~ about 66.6 mmol / cm ² based on nitrogen surface area of the modified pigment (e.g., about 8. 3 mmol / cm ² to about 40 mmol / cm ² ). While not intending to be bound by theory, it is believed that if the processing level of the modified pigment is too low, the dispersibility in an aqueous medium commonly used in ink compositions will not be sufficient. Furthermore, although not intending to be bound by theory, it is believed that if the processing level is too high, the ink composition containing the modified pigment does not solidify when it comes into contact with the paper, and may be rubbed and soiled. Yes.

  Although not intending to be bound by theory, it is believed that the average particle size of the pigment can be reduced by using a diazonium salt containing a 5-membered aromatic heterocycle. For example, the pigment prior to treatment with the diazonium salt described herein may have a first average particle size and the modified pigment may have a second average particle size that is less than the first average particle size. . The first average particle size may be at least about 140 nm (eg, at least about 200 nm, at least about 300 nm, at least about 400 nm, or at least about 500 nm), and the second average particle size may be at most about 130 nm (eg, at most about 120 nm, at most about 110 nm, at most about 100 nm, at most about 90 nm, at most about 80 nm, at most about 70 nm, or at most about 60 nm). While not intending to be bound by theory, modified pigments with a reduced average particle size improve the dispersibility exhibited in the ink composition and increase the gloss of images printed from ink compositions containing such pigments. It is thought that you can. Therefore, one advantage of modifying a pigment with the diazonium salts described herein is that a pigment with a small average particle size is used as a starting material, and that the average of the modified pigment is made mechanically after the modified pigment is made. Since reducing the particle size usually requires high costs, the production cost of the modified pigment having a small average particle size can be greatly reduced.

  The modified pigment formed above can be combined or mixed with a liquid vehicle to form an ink composition (eg, flexographic ink or inkjet ink composition). The liquid vehicle can be a solution, dispersion, slurry, or emulsion. The liquid vehicle can be an aqueous medium containing water (eg, deionized or distilled water) or a non-aqueous medium containing an organic medium (eg, alcohol). For example, the amount of water or organic medium in the ink composition can range from about 60% to about 95% (eg, from about 75% to about 90%) based on the weight of the ink composition. The flexographic ink composition can include the modified pigments, binders, and solvents described herein. Inkjet ink compositions can include the modified pigments described herein and an aqueous vehicle (eg, water or a water-containing mixture).

  Ink compositions contain suitable additives (eg, wetting agents, insecticides, binders, drying accelerators, penetrants, antifoaming agents, or surfactants) and are identified while maintaining the stability of the composition Of the desired properties. For example, the addition of a wetting agent can reduce the rate of water evaporation in the ink composition and minimize clogging of the print head nozzles. As the ink composition begins to dry, the concentration of wetting agent increases and evaporation further decreases. Wetting agents generally can also affect other properties of the ink composition and the printed images made with it, such as viscosity, pH, surface tension, optical density, and print quality. Such wetting agents generally include ethylene glycol, propylene glycol, diethylene glycols, glycerin, dipropylene glycols, polyethylene glycols, polypropylene glycols, alkanediols, amides, ethers, carboxylic acids, esters, alcohols. Organic sulfides, organic sulfoxides, sulfones, alcohol derivatives, 3-pyrrolidone, ether derivatives, amino alcohols, and ketones. The amount of a particular additive will vary depending on a variety of factors, including the molecular weight of the polymer, the viscosity, the amount of any ammonium salt added, as well as the nature of the polymer and the nature of any organic groups added to the pigment. .

  A printed image can be made from the ink composition described herein by incorporating the composition into a suitable printing device (eg, an ink jet printer) and generating an image on a substrate. Examples of suitable ink jet printers include thermal printers, piezoelectric printers, continuous printers, and valve jet printers. The image can be printed on any suitable substrate, such as plain paper, bond paper, coated paper, transparent material, textile material, plastic, polymer thin film, and inorganic substrate.

  The modified pigments described herein can also be used in aqueous paints such as paints or finishing materials. For example, paints can include liquid vehicles (eg, water or alcohol), modified pigments described herein, and resins. In addition, the modified pigments described herein can be used in toners, color filters, and electrophoretic displays. For example, the toner or color filter composition can include a modified pigment, resin, and one or more suitable additives as described herein. The electrophoretic display material may include a modifying material and a charge control agent as described herein.

  All publications, reference materials, applications, and patents referenced herein are hereby incorporated by reference in their entirety.

  The following examples are for illustrative purposes and are not intended to be limiting.

ビーカー中の粉砕した６．４ｇ（５０ｍｍｏｌ）の化合物１に、１ＭのＮａＯＨ溶液５２．５ｍｌと水１００ｍｌとを順次添加した。この混合物を、化合物１が完全に溶解するまで室温で撹拌した。２ＭのＮａＮＯ₂溶液２５ｍｌを添加した後、このようにして得た混合物を、蠕動ポンプを使って３０分以内に、２ＭのＨ₂ＳＯ₄４０ｍｌ、氷４０ｇ、および水１２５ｍｌの混合物に添加した。この工程の間、混合物の温度を５℃未満に維持した。添加が終了した後、ＫＩデンプン紙を使って過剰亜硝酸塩を点検し、結果が陰性であれば、２ＭのＮａＮＯ₂を２、３滴添加した。ジアゾニウム塩溶液（ジアゾニウム含有量約５０ｍｍｏｌ）を氷上に保ち、３０〜６０〜以内に使用した。 Example 1: Treatment of red pigment 122 with a diazonium salt from compound 1 and p-aminobenzoic acid (PABA) Diazotization of 2-aminotriazole-5-carboxylic acid (ie compound 1)

To 6.4 g (50 mmol) of crushed compound 1 in a beaker, 52.5 ml of 1M NaOH solution and 100 ml of water were sequentially added. The mixture was stirred at room temperature until compound 1 was completely dissolved. After adding 25 ml of 2M NaNO ₂ solution, the mixture thus obtained was added to a mixture of 40 ml of 2M H ₂ SO _4, 40 g of ice and 125 ml of water within 30 minutes using a peristaltic pump. During this step, the temperature of the mixture was maintained below 5 ° C. After the addition was completed, excess nitrite was checked using KI starch paper and if the result was negative, a few drops of 2M NaNO ₂ were added. A diazonium salt solution (diazonium content of about 50 mmol) was kept on ice and used within 30-60.

B. Treatment of red pigment 122 with diazonium salt derived from compound 1 and PABA 89 g of red pigment 122 press cake (containing 25 g of pigment) was placed in a 1 liter three-necked round bottom flask equipped with an overhead stirrer (Teflon blade). I put it in. The diazonium salt solution resulting from Step A was immediately added to the pigment and the mixture was stirred at about 100 RPM for 3 hours. A sample of the reaction mixture was tested with a H acid spot check to confirm the presence or absence of a diazonium salt. H acid spot check was performed as follows: 1 drop of H acid solution, ie 10 ml of 5% sodium bicarbonate solution, 0 H acid (ie 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid) .1 g dissolved was placed on a filter paper and a drop of the reaction mixture was placed beside it. When the clear runout of the reaction mixture contacts the H acid spot, a strong reddish purple appears if a diazonium salt is present in the reaction mixture. If the diazonium salt could not be found using the H acid spot check described above, the treatment of red pigment 122 was considered complete. After adjusting the pH of the reaction mixture to 9, the mixture was sonicated for 3 hours using a MISONIXS-4000 Ultrasound Liquid Processor. The dispersion thus obtained is subjected to diafiltration and purified with 5 volumes of deionized water until the conductivity of the permeate is below 200 μSiemens. At this point, the solid content of the dispersion was around 15%.

  The red pigment 122 was also treated with 6.7 g (50 mmol) of PABA (a primary amine containing a 6-membered aromatic ring) derived from a diazonium salt as a comparison.

Assuming that 1 mmol of sodium ion corresponds to 1 mmol of grafted anion, by measuring the sodium content of the final dispersion using an Orion-Ross sodium ion selective electrode connected to a millivolt meter (anhydrous basis), The incorporation of organic groups in the diazonium salt on the pigment surface was monitored. The average particle diameter of the modified red pigment 122 was measured with a NANO TRAC laser scatterometer. The sodium content and average particle size of the modified red pigment 122 are summarized in Table 2 below.

Results that M _v average particle size of the red pigment 122 modified with a diazonium salt derived from compound 1 were significantly smaller than M _v average particle size of the red pigment 122 modified with PABA from diazonium salt Show. The results further show that the diazonium salt from compound 1 has about 50% more organic groups attached to the surface of the red pigment 122 than the diazonium salt from PABA.

Example 2: Treatment of various pigments with a diazonium salt derived from Compound 1
Example 1 for four types of pigments: red pigment 122 (PR122), carbon black (BP700 grade from Cabot Corporation), blue pigment 15: 4 (PB15: 4), and yellow pigment 74 (PY74). After the procedure described in 1., treatment with a diazonium salt derived from compound 1 was performed. The average particle diameter M _v of PR122 was 300 nm. The results are shown in Table 2 below.

  The results show that the diazonium salt from Compound 1 effectively modified them by attaching organic groups to the surfaces of PR122, BP700, and PB15: 4. In addition, PR122 modified with the diazonium salt from compound 1 has a much smaller average particle size than the unmodified pigment.

  The results also show that the diazonium salt from compound 1 can be modified by attaching an organic group to the surface of PY74. Shakhnovich, “Dispersant Chemistry give up secrets”, Eur. Coatings J.H. , Issue 6, p. 28, (2006), yellow pigment 74 can be modified with a diazonium salt derived from a primary amine containing a 6-membered aromatic ring such as p-aminobenzenesulfonic acid and PABA. Can not.

Example 3: Treatment of red pigment 122 with a diazonium salt derived from compound 2
A 1-liter three-necked round-bottomed flask with an overhead stirrer (Teflon blade) is charged with 89.2 g of red pigment 122 presscake (containing 28% pigment (ie 25 g)), followed by 700 ml of deionized water. and put H ₂ SO ₄ 40 ml of 2M. After adding 4.2 g (50 mmol) of 3-amino-1,2,4-triazole (Compound 2), the mixture was stirred at room temperature for 45 minutes until the mixture became homogeneous. Then, with continued stirring, 25 ml of 2M sodium nitrite was added to the mixture over 5 minutes. Some bubbling was observed during the addition. After the addition of nitrite was completed, a H acid spot check was performed and a strong positive result was shown. Stirring was continued for 3 hours at room temperature, at which point the H acid spot check showed a negative result. The pH of the mixture was adjusted to 8 by adding 1M NaOH solution. The mixture was then sonicated for 3 hours using a MISONIX S-4000 Ultrasound Liquid Processor. The resulting dispersion was purified by diafiltration with 6 volumes of deionized water until the conductivity of the permeate was below 200μ Siemens. At this point, the solid content of the dispersion was around 13%. Thus a dispersion of magenta obtained is, M _v average particle size measured by NANO YRAC laser scattering meter was 167.2Nm. The modified pigment in the final dispersion (anhydrous basis) was 1,160 ppm.

Example 4: Treatment of various pigments with a diazonium salt from compound 3
In a 1 liter three-necked round bottom flask equipped with an overhead stirrer (Teflon blade), 256 g of yellow pigment 74 press cake (containing 37.3 g of pigment) was added, followed by 3- (2-amino-1, 3,4-thiadiazole -5-yl) propanoic acid (i.e., compound 3) and 7.68 g (44.4 mmol), and placed 219ml of H ₂ SO ₄ of 2M. The mixture was stirred for 45 minutes to a homogeneous mixture, which was cooled to around 0 ° C. with an ice bath. When this temperature was reached, a peristaltic pump was used to add 23 ml of 2M sodium nitrite solution over 20 minutes. Some bubbling was observed and a H acid spot check at the end of the addition showed a strong positive result. When this mixture was continuously stirred at 0 ° C. for 3 hours, the result of H acid spot check became negative. After filtration of the reaction mixture, the modified yellow pigment precipitate was thoroughly washed with 600 ml of deionized water. The precipitate was then mixed with 500 ml of deionized water and the pH of the mixture was adjusted to 8 by adding 1M NaOH solution. To age the pigment, the mixture was heated at 80 ° C. for 1 hour and then sonicated for 3 hours using a MISONIX S-4000 Ultrasound Liquid Processor. The resulting dispersion was purified by diafiltration with 6 volumes of deionized water until the conductivity of the permeate was below 200 μSiemens. At this point, the solid content of the dispersion was around 18%. This was centrifuged at 4,500 rpm for 30 minutes to remove large particles.

Red pigment 122, BP700, and blue pigment 15: 4 were also treated with the diazonium salt from compound 3 using the procedure described above. The average particle diameter M _v of PR122 was 300nm.

The average particle size and sodium content of the final dispersion (anhydrous basis) of this series of modified pigments were measured. The results are summarized in Table 3 below.

  The results indicate that the diazonium salt from compound 3 effectively modified them by attaching organic groups to the surfaces of PR122, BP700, and PB15: 4. The results also show that the diazonium salt derived from compound 3 is also effectively modified with a diazonium salt derived from a primary amine containing a 6-membered aromatic ring such as p-aminobenzenesulfonic acid and PY74 that cannot be modified with PABA. It also shows that it was made.

ビーカー中の３．９９ｇ（３０ｍｍｏｌ）の化合物１１に３５ｍｌの１Ｍ Ｈ₂ＳＯ₄を添加した。次に、この混合物に、蠕動ポンプを使い、室温で３０分間にわたって２ＭのＮａＮＯ₂溶液１５．５ｍｌを添加した。このようにして得た混合物を３０分間撹拌した時点で、ＫＩデンプン紙を使って過剰な亜硝酸塩を点検し、結果が陰性の場合は２ＭのＮａＮＯ₂を２、３滴添加しえた。このようにして形成されたジアゾニウム塩の分散液（ジアゾニウム含有量が約３０ｍｍｏｌ）は、室温で４〜６時間保存しても分解しない。 Example 5: Treatment of various pigments with the diazonium salt from compound 11 Diazotization of 2-aminoimidazole-4,5-dinitrile (Compound 11)

To 3.99 g (30 mmol) of compound 11 in a beaker was added 35 ml of 1 MH ₂ SO ₄ . Next, 15.5 ml of 2M NaNO ₂ solution was added to the mixture using a peristaltic pump over 30 minutes at room temperature. When the resulting mixture was stirred for 30 minutes, excess nitrite was checked using KI starch paper, and if the result was negative, a few drops of 2M NaNO ₂ could be added. The diazonium salt dispersion thus formed (diazonium content is about 30 mmol) does not decompose even when stored at room temperature for 4 to 6 hours.

B. Treatment of various pigments with diazonium salts derived from compound 11 A two liter three-necked round bottom flask equipped with an overhead stirrer (Teflon blade) was charged with red pigment 122 presscake (PR122; 28% pigment (ie , 60 g))), followed by 214 g of water and the diazonium salt solution produced in stage A. The mixture was stirred at about 100 rpm for 30 minutes and then heated at 60 ° C. and kept at this temperature for 45 minutes. At this point, the H acid spot check showed a negative result, indicating that the diazonium salt was completely extinguished by the reaction. Next, the pH of the reaction slurry was raised to 9 using 1M sodium hydroxide solution, and the slurry was sonicated for 3 hours using a MISONIX S-4000 Ultrasound Liquid Processor. The resulting mixture was purified by diafiltration with 6 volumes of deionized water until the conductivity of the permeate was below 200 μSiemens. At this point, the solid content of the dispersion was around 15%. Next, the dispersion was centrifuged at 4,500 rpm for 30 minutes to remove large particles.

Treatment of blue pigment 15: 4 (PB15: 4) and yellow pigment 74 (PY74) with compound 11 was carried out in a manner different from that described above. The results are summarized in Table 4 below.

As shown in Table 4, the diazonium salt derived from Compound 11 was effectively modified by bonding organic groups to the surfaces of PR122, PB15: 4, and PY74. In addition, the pretreatment, the average particle size M _v of the three types of pigment was in the range of 400 nm to 700 nm. As shown in Table 4, the diazonium salt derived from Compound 11 significantly reduced the average particle size of these three types of pigments.

Example 6: Treatment of various pigments with diazonium salts derived from compound 12 Red pigment 122 and BP700 were treated with diazonium salts derived from compound 12. The procedure was almost the same as in Example 4, but only 2M H ₂ SO ₄ was replaced with 2 equivalents of nitrous acid.

  The average particle diameter of the modified pigment and the sodium content of the modified pigment in the final dispersion (anhydrous basis) were measured. The results are summarized in Table 5 below.

表５に示す通り、化合物１２由来のジアゾニウム塩は、ＰＲ１２２およびＢＰ７００を、その表面に有機基を結合させて平均粒径の小さい変性顔料を得ることによって有効に変性させた。

As shown in Table 5, the diazonium salt derived from Compound 12 effectively modified PR122 and BP700 by binding a organic group to the surface to obtain a modified pigment having a small average particle size.

Example 7: Treatment of red pigment 122 with a diazonium salt derived from compound 13
In a stainless steel beaker, 107 g of red pigment 122 press cake (containing 30 g of pigment) was added followed by 6.51 g of 2-aminotriazole-4-sulfonic acid (ie, compound 13) and 350 g of deionized water. . After homogenizing the mixture at 6,500 rpm using a SILVERSON L4RT-A rotor-stator high shear mixer, a solution of 2.54 g NaNO _{2 in} 20 ml deionized water was added dropwise within 10 minutes. Mixing was continued for 2 hours. At the end of this period, the temperature reached 70 ° C. due to heat release during mixing (no external heat was used). After adjusting the pH of the mixture to 4.0 with 1 M NaOH solution, the mixture thus formed was purified with 5 volumes of deionized water until the conductivity of the permeate was below 200 μSiemens. At this point, the solid content of the dispersion was around 16%. The dispersion was sonicated for 1 hour using a MISONIX S-4000 Ultrasound Liquid Processor and centrifuged at 4,500 rpm for 20 minutes to remove large particles. Dispersion of reddish violet obtained in this manner had an average particle diameter M _v as measured by NANOTRAC laser scattering meter was 90 nm.

For comparison, the red pigment 122 was also treated with diazonium salts derived from p-aminobenzenesulfonic acid and p-aminobenzoic acid. The method used was the same as described above, but when the red pigment 122 was treated with a diazonium salt derived from p-aminobenzoic acid, 2 equivalents of nitrous acid were added to the reaction mixture before adding NaNO ₂ . .

As a result, it is possible to prepare a modified pigment having a very small particle diameter by treating the pigment with a diazonium salt derived from the compound 13 (that is, a primary amine containing a 5-membered aromatic heterocycle). Is shown. In contrast, when the pigment was treated with a diazonium salt derived from p-aminobenzenesulfonic acid and p-aminobenzoic acid (ie, a primary amine containing a 6-membered aromatic ring), it was obtained in this way. the average particle diameter M _v of the modified pigment is not less than 125～135Nm.

Example 8: Treatment of various pigments with diazonium salts derived from compound 13
Four types of pigments, red pigment 122 (PR122), blue pigment 15: 4 (PB15: 4), and BP700 were treated with the diazonium salt from compound 13 according to the procedure described in Example 7. The results are shown in Table 6 below.

  As a result, the diazonium salt derived from compound 13 effectively modified these pigments by binding organic groups to the surfaces of PR122, PB15: 4, and BP700 to obtain a modified pigment having a small average particle diameter. Is shown.

の化合物であり、式中、
ＸはＯ、Ｎ（Ｒ _a ）、またはＳであり、
Ｒ ₁ はＨ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₂ −Ｃ ₁₀ アルケニル、Ｃ ₂ −Ｃ ₁₀ アルキニル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルケニル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ _b 、ＣＯＯＲ _b 、ＯＣ（Ｏ）Ｒ _b 、Ｃ（Ｏ）Ｒ _b 、Ｃ（Ｏ）ＮＲ _b Ｒ _c 、ＳＯ ₃ Ｒ _c 、ＮＲ _b Ｒ _c 、またはＮ ⁺ （Ｒ _b Ｒ _c Ｒ _d ）Ｙであり、
Ｒ _a 、Ｒ _b 、Ｒ _c 、およびＲ _d は、それぞれ独立して、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、アリール、またはヘテロアリールであり、Ｙは陰イオンである、項目３に記載の方法。
（７）
Ｒ ₁ は、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、ＣＯＯＲ _a 、Ｃ（Ｏ）ＮＨ（Ｃ ₁ −Ｃ ₁₀ アルキル）、またはＣ ₁ −Ｃ ₁₀ アルキルで任意に置換されたフェニルであり、ここで、Ｃ ₁ −Ｃ ₁₀ アルキルは、フルオロ、ＯＲ _a 、ＣＯＯＲ _a 、またはＮ ⁺ （Ｒ _b Ｒ _c Ｒ _d ）で任意に置換される、項目６に記載の方法。
（８）
前記１級アミンは、

である、項目７に記載の方法。
（９）
前記５員芳香族複素環は、２つの環内ヘテロ原子を含み、そのうち少なくとも１つが窒素原子である、項目１に記載の方法。
（１０）
前記１級アミンは、イミダゾリル、ピラゾリル、チアゾリル、イソチアゾリル、オキサゾリル、またはイソオキサゾリルを含む、項目９に記載の方法。
（１１）
前記１級アミンは、イミダゾリルまたはチアゾリルを含む、項目１０に記載の方法。
（１２）
前記１級アミンは、式（ＩＩ）

の化合物であり、式中、
ＸはＯ、Ｎ（Ｒ _a ）、またはＳであり、
Ｒ ₁ およびＲ ₂ は、それぞれ独立して、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₂ −Ｃ ₁₀ アルケニル、Ｃ ₂ −Ｃ ₁₀ アルキニル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルケニル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ _b 、ＣＯＯＲ _b 、ＯＣ（Ｏ）Ｒ _b 、Ｃ（Ｏ）Ｒ _b 、Ｃ（Ｏ）ＮＲ _b Ｒ _c 、ＳＯ ₃ Ｒ _c 、ＮＲ _b Ｒ _c 、またはＮ ⁺ （Ｒ _b Ｒ _c Ｒ _d ）Ｙであり、
Ｒ _a 、Ｒ _b 、Ｒ _c 、およびＲ _d は、それぞれ独立して、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、アリール、またはヘテロアリールであり、Ｙは陰イオンである、項目９に記載の方法。
（１３）
Ｒ ₁ およびＲ ₂ は、それぞれ独立して、Ｈ、シアノ、ＣＯＯＲ _a 、またはＳＯ ₃ Ｒ _a である、項目１２に記載の方法。
（１４）
前記１級アミンは、

である、項目１３に記載の方法。
（１５）
前記５員芳香族複素環は、４つの環内ヘテロ原子を含み、そのうち少なくとも３つが窒素原子である、項目１に記載の方法。
（１６）
前記１級アミンは、テトラゾリルを含む、項目１５に記載の方法。
（１７）
前記１級アミンは、

である、項目１５に記載の方法。
（１８）
前記顔料は、黄色顔料１、７４、１５５、１８０、１８５、２１３、２１８、２２０、もしくは２２１、赤色顔料１２２、２０２、２５４、もしくは２６９、青色顔料１５、１６、もしくは６０、または紫色顔料１９を含む、項目１に記載の方法。
（１９）
前記５員芳香族複素環は、前記変性顔料の窒素表面積に基づいて約２．７ｍｍｏｌ／ｃｍ ² 〜約６６．６ｍｍｏｌ／ｃｍ ² の処理レベルで前記変性顔料の表面に存在する、項目１に記載の方法。
（２０）
前記顔料は、第１の平均粒子直径を有し、前記変性材料は、前記第１の平均粒子直径より小さい第２の平均粒子直径を有する、項目１に記載の方法。
（２１）
前記第１の平均粒子直径は、最小でも約１４０ｎｍであり、前記第２の平均粒子直径が最大でも約１３０ｎｍである、項目２０に記載の方法。
（２２）
前記変性顔料を液体ビヒクルに取り込んで、インクジェット用インク組成物を形成することをさらに含む、項目１に記載の方法。
（２３）
顔料を、５員芳香族複素環と前記５員芳香族複素環に直接結合したジアゾニウム基とを含むジアゾニウム塩と反応させ、それによって前記５員芳香族複素環を含む変性顔料を形成することを含む方法であって、
前記５員芳香族複素環は３つの環内ヘテロ原子を含み、そのうち少なくとも２つが窒素原子である、方法。
（２４）
前記ジアゾニウム塩は、１，２，４−トリアゾリル、１，２，３−トリアゾリル、１，３，４−チアジアゾリル、１，２，４−チアジアゾリル、１，２，３−チアジアゾリル、１，２，５−チアジアゾリル、１，３，４−オキサジアゾリル、１，２，４−オキサジアゾリル、１，２，３−オキサジアゾリル、または１，２，５−オキサジアゾリルを含む、項目２３に記載の方法。
（２５）
前記ジアゾニウム塩は、１，２，４−トリアゾリル、または１，３，４−チアジアゾリルを含む、項目２４に記載の方法。
（２６）
前記ジアゾニウム塩は、式（Ｉａ）

の陽イオンを含み、式中、
ＸはＯ、Ｎ（Ｒ _a ）、またはＳであり、
Ｒ ₁ は、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₂ −Ｃ ₁₀ アルケニル、Ｃ ₂ −Ｃ ₁₀ アルキニル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルケニル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ _b 、ＣＯＯＲ _b 、ＯＣ（Ｏ）Ｒ _b 、Ｃ（Ｏ）Ｒ _b 、Ｃ（Ｏ）ＮＲ _b Ｒ _c 、ＳＯ ₃ Ｒ _c 、ＮＲ _b Ｒ _c 、またはＮ ⁺ （Ｒ _b Ｒ _c Ｒ _d ）Ｙであり、
Ｒ _a 、Ｒ _b 、Ｒ _c 、およびＲ _d は、それぞれ独立して、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、アリール、またはヘテロアリールであり、Ｙは陰イオンである、項目２３に記載の方法。
（２７）
Ｒ ₁ は、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、ＣＯＯＲ _a 、Ｃ（Ｏ）ＮＨ（Ｃ ₁ −Ｃ ₁₀ アルキル）、Ｃ ₁ −Ｃ ₁₀ アルキルで任意に置換されたフェニルであり、ここでＣ ₁ −Ｃ ₁₀ アルキルは、フルオロ、ＯＲ _a 、ＣＯＯＲ _a 、ＮＲ _b Ｒ _c 、またはＮ ⁺ （Ｒ _b Ｒ _c Ｒ _d ）で任意に置換される、項目２６に記載の方法。
（２８）
前記ジアゾニウム塩は、

を含む、項目２７に記載の方法。
（２９）
顔料を、５員芳香族複素環を含むジアゾニウム塩と反応させ、それによって前記５員芳香族複素環を含む変性顔料を形成することを含む方法であって、
前記ジアゾニウム塩は式（ＩＩａ）

の陽イオンを含み、
式中、
ＸはＯ、Ｎ（Ｒ _a ）、またはＳであり、
Ｒ ₁ およびＲ ₂ は、それぞれ独立して、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₂ −Ｃ ₁₀ アルケニル、Ｃ ₂ −Ｃ ₁₀ アルキニル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルケニル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ _b 、ＣＯＯＲ _b 、ＯＣ（Ｏ）Ｒ _b 、Ｃ（Ｏ）Ｒ _b 、Ｃ（Ｏ）ＮＲ _b Ｒ _c 、ＳＯ ₃ Ｒ _c 、ＮＲ _b Ｒ _c 、またはＮ ⁺ （Ｒ _b Ｒ _c Ｒ _d ）Ｙであり、
Ｒ _a 、Ｒ _b 、Ｒ _c 、およびＲ _d は、それぞれ独立して、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、アリール、またはヘテロアリールであり、Ｙは陽イオンであるが、ただし、Ｒ ₁ およびＲ ₂ の内少なくとも１つはＨではない、方法。
（３０）
Ｒ ₁ およびＲ ₂ は、それぞれ独立してＨ、シアノ、ＣＯＯＲ _a 、またはＳＯ ₃ Ｒ _a である、項目２９に記載の方法。
（３１）
前記ジアゾニウム塩は、

を含む、項目３０に記載の方法。
（３２）
液体ビヒクルと、
顔料および前記顔料に結合した有機基を含む材料であって、前記有機基はただ１つの芳香環を含み、前記ただ１つの芳香環は５員芳香族複素環である材料と、
を含むインク組成物であって、
前記５員芳香族複素環は３つの環内ヘテロ原子を含み、そのうち少なくとも２つは窒素原子である、インク組成物。
（３３）
前記有機基は、１，２，４−トリアゾリル、１，２，３−トリアゾリル、１，３，４−チアジアゾリル、１，２，４−チアジアゾリル、１，２，３−チアジアゾリル、１，２，５−チアジアゾリル、１，３，４−オキサジアゾリル、１，２，４−オキサジアゾリル、１，２，３−オキサジアゾリル、または１，２，５−オキサジアゾリルを含む、項目３２に記載の組成物。
（３４）
前記有機基は、１，２，４−トリアゾリルまたは１，３，４−チアジアゾリルを含む、項目３３に記載の組成物。
（３５）
前記有機基は、式（Ｉｂ）

の有機基であり、式中、
ＸはＯ、Ｎ（Ｒ _a ）、またはＳであり、
Ｒ ₁ は、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₂ −Ｃ ₁₀ アルケニル、Ｃ ₂ −Ｃ ₁₀ アルキニル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルケニル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ _b 、ＣＯＯＲ _b 、ＯＣ（Ｏ）Ｒ _b 、Ｃ（Ｏ）Ｒ _b 、Ｃ（Ｏ）ＮＲ _b Ｒ _c 、ＳＯ ₃ Ｒ _c 、ＮＲ _b Ｒ _c 、またはＮ ⁺ （Ｒ _b Ｒ _c Ｒ _d ）Ｙであり、
Ｒ _a 、Ｒ _b 、Ｒ _c 、およびＲ _d は，それぞれ独立して、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、アリール、またはヘテロアリールであり、
Ｙは陰イオンである、項目３２に記載の組成物。
（３６）
Ｒ ₁ は、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、ＣＯＯＲ _a 、Ｃ（Ｏ）ＮＨ（Ｃ ₁ −Ｃ ₁₀ アルキル）、Ｃ ₁ −Ｃ ₁₀ アルキルで任意に置換されたフェニルであり、ここでＣ ₁ −Ｃ ₁₀ アルキルは、フルオロ、ＯＲ _a 、ＣＯＯＲ _a 、ＮＲ _b Ｒ _c 、またはＮ ⁺ （Ｒ _b Ｒ _c Ｒ _d ）で任意に置換される、項目３５に記載の組成物。
（３７）
前記有機基は、

である、項目３６に記載の組成物。
（３８）
前記材料は、黄色顔料１、７４、１５５、１８０、１８５、２１３、２１８、２２０、もしくは２２１、赤色顔料１２２、２０２、２５４、もしくは２６９、青色顔料１５、１６、もしくは６０、または紫色顔料１９を含む、項目３２に記載の組成物。
（３９）
顔料と、
前記顔料に結合した有機基であって、ただ１つの芳香環を含み、前記ただ１つの芳香環は５員芳香族複素環である有機基と
を含む組成物であって、
前記５員芳香族複素環は３つの環内ヘテロ原子を含み、そのうち少なくとも２つは窒素原子である、組成物。
（４０）
項目３９に記載の組成物を含む物品であって、インクジェットプリンター、コーティング、ペイント、トナー、カラーフィルター、または電気泳動ディスプレイである、物品。
（４１）
液体ビヒクルと、
顔料および前記顔料に結合した式（ＩＩｂ）

で表わされる有機基を含む材料と、
を含むインク組成物であって、式中、
Ｘは、Ｏ、Ｎ（Ｒ _a ）、またはＳであり、
Ｒ ₁ およびＲ ₂ は、それぞれ独立して、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₂ −Ｃ ₁₀ アルケニル、Ｃ ₂ −Ｃ ₁₀ アルキニル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルケニル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ _b 、ＣＯＯＲ _b 、ＯＣ（Ｏ）Ｒ _b 、Ｃ（Ｏ）Ｒ _b 、Ｃ（Ｏ）ＮＲ _b Ｒ _c 、ＳＯ ₃ Ｒ _c 、ＮＲ _b Ｒ _c 、またはＮ ⁺ （Ｒ _b Ｒ _c Ｒ _d ）Ｙであり、
Ｒ _a 、Ｒ _b 、Ｒ _c 、およびＲ _d は、それぞれ独立して、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、アリール、またはヘテロアリールであり、Ｙは陰イオンであるが、ただし、Ｒ ₁ およびＲ ₂ の内の少なくとも１つはＨではない、インク組成物。
（４２）
Ｒ ₁ は、Ｈ、シアノ、ＣＯＯＲ _a 、またはＳＯ ₃ Ｒ _a であり、Ｒ ₂ は、シアノ、ＣＯＯＲ _a 、またはＳＯ ₃ Ｒ _a である、項目４１に記載の組成物。
（４３）
前記有機基は、

である、項目４２に記載の組成物。
（４４）
前記材料は、黄色顔料１、７４、１５５、１８０、１８５、２１３、２１８、２２０、もしくは２２１、赤色顔料１２２、２０２、２５４、もしくは２６９、青色顔料１５、１６、もしくは６０、または紫色顔料１９を含む、項目４１に記載の組成物。
（４５）
顔料と、
前記顔料に結合し、式（ＩＩｂ）

で表わされる有機基と、を含む組成物であって、
式中、
Ｘは、Ｏ、Ｎ（Ｒ _a ）、またはＳであり、
Ｒ ₁ およびＲ ₂ は、それぞれ独立してＨ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₂ −Ｃ ₁₀ アルケニル、Ｃ ₂ −Ｃ ₁₀ アルキニル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルケニル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルケニル、アリール、ヘテロアリール、ハロ、シアノ、ＯＲ _b 、ＣＯＯＲ _b 、ＯＣ（Ｏ）Ｒ _b 、Ｃ（Ｏ）Ｒ _b 、Ｃ（Ｏ）ＮＲ _b Ｒ _c 、ＳＯ ₃ Ｒ _c 、ＮＲ _b Ｒ _c 、またはＮ ⁺ （Ｒ _b Ｒ _c Ｒ _d ）Ｙであり、
Ｒ _a 、Ｒ _b 、Ｒ _c 、およびＲ _d は、それぞれ独立して、Ｈ、Ｃ ₁ −Ｃ ₁₀ アルキル、Ｃ ₃ −Ｃ ₂₀ シクロアルキル、Ｃ ₁ −Ｃ ₂₀ ヘテロシクロアルキル、アリール、またはヘテロアリールであり、Ｙは陰イオンであるが、ただし、Ｒ ₁ およびＲ ₂ の内の少なくとも１つはＨではない、組成物。
（４６）
項目４５に記載の組成物を含む物品であって、インクジェットプリンター、コーティング、ペイント、トナー、カラーフィルター、または電気泳動ディスプレイである、物品。
（４７）
液体ビヒクルと、
顔料および前記顔料に結合した有機基を含む材料であって、前記有機基が５員芳香族複素環を含む材料と
を含むインク組成物であって、
前記５員芳香族複素環は４つの環内ヘテロ原子を含み、そのうち少なくとも３つは窒素原子である、
インク組成物。
（４８）
前記有機基は、テトラゾリルを含む、項目４７に記載の組成物。
（４９）
前記有機基は、

である、項目４７に記載の組成物。
（５０）
前記変性顔料は、黄色顔料１、７４、１５５、１８０、１８５、２１３、２１８、２２０、もしくは２２１、赤色顔料１２２、２０２、２５４、もしくは２６９、青色顔料１５、１６、もしくは６０、または紫色顔料１９を含む、項目４７に記載の組成物。
（５１）
顔料と、
前記顔料に結合された有機基であって、５員芳香族複素環を含む有機基と、を含む組成物であって、
前記５員芳香族複素環は４つの環内ヘテロ原子を含み、そのうち少なくとも３つは窒素原子である、組成物。
（５２）
項目５１に記載の組成物を含む物品であって、インクジェットプリンター、コーティング、ペイント、トナー、カラーフィルター、または電気泳動ディスプレイである、物品。 Other embodiments are in the claims.
The present invention also includes the following contents.
(1)
A diazotizing agent is reacted with a primary amine containing a 5-membered aromatic heterocycle and an amino group directly bonded to the 5-membered aromatic heterocycle, thereby containing a diazonium salt containing the 5-membered aromatic heterocycle Forming a reaction mixture, and
After the diazonium salt is formed, adding a pigment to the reaction mixture, thereby forming a modified pigment comprising the 5-membered aromatic heterocycle;
A method comprising:
The method wherein the 5-membered aromatic heterocycle contains at least two endocyclic heteroatoms, at least one of which is a nitrogen atom.
(2)
The method of item 1, wherein the primary amine is reacted with the diazotizing agent at a pH of at most about 2.5.
(3)
The method according to item 1, wherein the 5-membered aromatic heterocycle contains three intra-ring heteroatoms, at least two of which are nitrogen atoms.
(4)
The primary amine is 1,2,4-triazolyl, 1,2,3-triazolyl, 1,3,4-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,3-thiadiazolyl, 1,2, 4. The method of item 3, comprising 5-thiadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-oxadiazolyl, or 1,2,5-oxadiazolyl.
(5)
Item 5. The method according to Item 4, wherein the primary amine comprises 1,2,4-triazolyl or 1,3,4-thiadiazolyl.
(6)
The primary amine has the formula (I)

A compound of the formula:
X is O, N (R _a ), or S;
R ₁ is H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl, C ₁ -C ₂₀ heterocycloalkyl. , C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, _{cyano, OR b, COOR b, OC} (O) R b, C (O) R b, C (O) NR b R c, SO 3 R _c , NR _b R _c , or N ⁺ (R _b R _c R _d ) Y,
R _a , R _b , R _c and R _d are each independently H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, or heteroaryl. Item 4. The method according to Item 3, wherein Y is an anion.
(7)
R ₁ is H, C ₁ -C ₁₀ alkyl, COOR _a , C (O) NH (C ₁ -C ₁₀ alkyl), or phenyl optionally substituted with C ₁ -C ₁₀ alkyl, wherein C ₁ -C ₁₀ alkyl, fluoro, oR _a, COOR _a, or ^{_{N + (R b R c R}} d) with optionally substituted the method of claim 6,.
(8)
The primary amine is

The method according to item 7, wherein
(9)
The method according to item 1, wherein the 5-membered aromatic heterocycle contains two endocyclic heteroatoms, at least one of which is a nitrogen atom.
(10)
10. A method according to item 9, wherein the primary amine comprises imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, or isoxazolyl.
(11)
Item 11. The method according to Item 10, wherein the primary amine comprises imidazolyl or thiazolyl.
(12)
The primary amine has the formula (II)

A compound of the formula:
X is O, N (R _a ), or S;
R ₁ and R ₂ are each independently H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl. , C ₁ -C ₂₀ heterocycloalkyl, C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, cyano, OR _b , COOR _b , OC (O) R _b , C (O) R _b , C ( O) a _{NR b R c, SO 3 R} c, NR b R c or ^{_{N + (R b R c R}} d) Y,,
R _a , R _b , R _c and R _d are each independently H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, or heteroaryl. 10. The method according to item 9, wherein Y is an anion.
(13)
13. The method according to item 12, wherein R ₁ and R ₂ are each independently H, cyano, COOR _a , or SO ₃ R _a .
(14)
The primary amine is

14. The method according to item 13, wherein
(15)
The method according to item 1, wherein the 5-membered aromatic heterocycle contains 4 intra-ring heteroatoms, at least 3 of which are nitrogen atoms.
(16)
16. A method according to item 15, wherein the primary amine comprises tetrazolyl.
(17)
The primary amine is

The method according to item 15, wherein
(18)
The pigment includes yellow pigment 1, 74, 155, 180, 185, 213, 218, 220, or 221, red pigment 122, 202, 254, or 269, blue pigment 15, 16, or 60, or purple pigment 19. The method of item 1, comprising.
(19)
The 5-membered heteroaromatic ring is present in the modified pigment based on nitrogen surface area of about 2.7 mmol / cm ² ~ surface of the modified pigment of about 66.6 mmol / cm ² of the processing level, claim 1 the method of.
(20)
Item 2. The method of item 1, wherein the pigment has a first average particle diameter and the modifying material has a second average particle diameter that is less than the first average particle diameter.
(21)
21. The method of item 20, wherein the first average particle diameter is at least about 140 nm and the second average particle diameter is at most about 130 nm.
(22)
The method of item 1, further comprising incorporating the modified pigment into a liquid vehicle to form an ink-jet ink composition.
(23)
Reacting a pigment with a diazonium salt comprising a 5-membered aromatic heterocycle and a diazonium group bonded directly to the 5-membered aromatic heterocycle, thereby forming a modified pigment comprising the 5-membered aromatic heterocycle A method comprising:
The method wherein the 5-membered aromatic heterocycle contains three endocyclic heteroatoms, at least two of which are nitrogen atoms.
(24)
The diazonium salt is 1,2,4-triazolyl, 1,2,3-triazolyl, 1,3,4-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,3-thiadiazolyl, 1,2,5. 24. The method of item 23, comprising thiadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-oxadiazolyl, or 1,2,5-oxadiazolyl.
(25)
25. A method according to item 24, wherein the diazonium salt comprises 1,2,4-triazolyl, or 1,3,4-thiadiazolyl.
(26)
The diazonium salt has the formula (Ia)

Of the formula, wherein
X is O, N (R _a ), or S;
R ₁ is H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl, C ₁ -C ₂₀ heterocyclo. alkyl, C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, _{cyano, OR b, COOR b, OC} (O) R b, C (O) R b, C (O) NR b R c, SO ₃ R _c , NR _b R _c , or N ⁺ (R _b R _c R _d ) Y,
R _a , R _b , R _c and R _d are each independently H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, or heteroaryl. 24. The method of item 23, wherein Y is an anion.
(27)
R ₁ is H, C ₁ -C ₁₀ alkyl, COOR _a , C (O) NH (C ₁ -C ₁₀ alkyl), phenyl optionally substituted with C ₁ -C ₁₀ alkyl, where C ₁ -C ₁₀ alkyl, _{fluoro, oR a, COOR a, NR} b R c or ^{_{N + (R b R c R}} d) with optionally substituted method of claim 26,.
(28)
The diazonium salt is

The method according to item 27, comprising:
(29)
Reacting a pigment with a diazonium salt containing a 5-membered aromatic heterocycle, thereby forming a modified pigment containing the 5-membered aromatic heterocycle, comprising:
The diazonium salt has the formula (IIa)

Containing cations
Where
X is O, N (R _a ), or S;
R ₁ and R ₂ are each independently H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl. , C ₁ -C ₂₀ heterocycloalkyl, C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, cyano, OR _b , COOR _b , OC (O) R _b , C (O) R _b , C ( O) a _{NR b R c, SO 3 R} c, NR b R c or ^{_{N + (R b R c R}} d) Y,,
R _a , R _b , R _c and R _d are each independently H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, or heteroaryl. Wherein Y is a cation, provided that at least one of R ₁ and R ₂ is not H.
(30)
30. The method of item 29, wherein R ₁ and R ₂ are each independently H, cyano, COOR _a , or SO ₃ R _a .
(31)
The diazonium salt is

The method according to item 30, comprising:
(32)
Liquid vehicle,
A material comprising a pigment and an organic group bonded to the pigment, wherein the organic group comprises only one aromatic ring, wherein the only aromatic ring is a 5-membered aromatic heterocycle;
An ink composition comprising:
The ink composition according to claim 5, wherein the 5-membered aromatic heterocycle contains three intracyclic heteroatoms, at least two of which are nitrogen atoms.
(33)
The organic group is 1,2,4-triazolyl, 1,2,3-triazolyl, 1,3,4-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,3-thiadiazolyl, 1,2,5. 33. A composition according to item 32 comprising thiadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-oxadiazolyl, or 1,2,5-oxadiazolyl.
(34)
34. The composition of item 33, wherein the organic group comprises 1,2,4-triazolyl or 1,3,4-thiadiazolyl.
(35)
The organic group has the formula (Ib)

An organic group of the formula
X is O, N (R _a ), or S;
R ₁ is H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl, C ₁ -C ₂₀ heterocyclo. alkyl, C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, _{cyano, OR b, COOR b, OC} (O) R b, C (O) R b, C (O) NR b R c, SO ₃ R _c , NR _b R _c , or N ⁺ (R _b R _c R _d ) Y,
R _a , R _b , R _c and R _d are each independently H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, or heteroaryl. And
33. A composition according to item 32, wherein Y is an anion.
(36)
R ₁ is H, C ₁ -C ₁₀ alkyl, COOR _a , C (O) NH (C ₁ -C ₁₀ alkyl), phenyl optionally substituted with C ₁ -C ₁₀ alkyl, where C ₁ -C ₁₀ alkyl, _{fluoro, oR a, COOR a, NR} b R c or ^{_{N + (R b R c R}} d) with optionally substituted composition of claim 35.
(37)
The organic group is

37. The composition according to item 36, wherein
(38)
The materials include yellow pigment 1, 74, 155, 180, 185, 213, 218, 220, or 221, red pigment 122, 202, 254, or 269, blue pigment 15, 16, or 60, or purple pigment 19. 33. The composition of item 32 comprising.
(39)
Pigments,
An organic group bonded to the pigment, the organic group containing only one aromatic ring, wherein the only aromatic ring is a 5-membered aromatic heterocyclic ring;
A composition comprising:
The composition wherein the 5-membered aromatic heterocycle contains 3 endocyclic heteroatoms, at least 2 of which are nitrogen atoms.
(40)
40. An article comprising the composition of item 39, wherein the article is an inkjet printer, coating, paint, toner, color filter, or electrophoretic display.
(41)
Liquid vehicle,
Pigment and formula (IIb) bound to said pigment

A material containing an organic group represented by:
An ink composition comprising:
X is O, N (R _a ), or S;
R ₁ and R ₂ are each independently H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl. , C ₁ -C ₂₀ heterocycloalkyl, C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, cyano, OR _b , COOR _b , OC (O) R _b , C (O) R _b , C ( O) a _{NR b R c, SO 3 R} c, NR b R c or ^{_{N + (R b R c R}} d) Y,,
R _a , R _b , R _c and R _d are each independently H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, or heteroaryl. And Y is an anion, provided that at least one of R ₁ and R ₂ is not H.
(42)
R ₁ is H, cyano, COOR _a or SO ₃ R _a,, R ₂ is cyano, COOR _a or SO ₃ is R _a, composition of claim 41.
(43)
The organic group is

43. A composition according to item 42, wherein
(44)
The materials include yellow pigment 1, 74, 155, 180, 185, 213, 218, 220, or 221, red pigment 122, 202, 254, or 269, blue pigment 15, 16, or 60, or purple pigment 19. 42. The composition of item 41 comprising.
(45)
Pigments,
Bonded to the pigment, formula (IIb)

An organic group represented by the formula:
Where
X is O, N (R _a ), or S;
R ₁ and R ₂ are each independently H, C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl, C ₂ -C ₁₀ alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₃ -C ₂₀ cycloalkenyl, C ₁ -C ₂₀ heterocycloalkyl, C ₁ -C ₂₀ heterocycloalkenyl, aryl, heteroaryl, halo, cyano, OR _b , COOR _b , OC (O) R _b , C (O) R _b , C (O ) NR _b R _c , SO ₃ R _c , NR _b R _c , or N ⁺ (R _b R _c R _d ) Y,
R _a , R _b , R _c and R _d are each independently H, C ₁ -C ₁₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₁ -C ₂₀ heterocycloalkyl, aryl, or heteroaryl. And Y is an anion, provided that at least one of R ₁ and R ₂ is not H.
(46)
46. An article comprising the composition of item 45, wherein the article is an inkjet printer, coating, paint, toner, color filter, or electrophoretic display.
(47)
Liquid vehicle,
A material containing a pigment and an organic group bonded to the pigment, wherein the organic group contains a 5-membered aromatic heterocyclic ring;
An ink composition comprising:
The 5-membered aromatic heterocycle contains four endocyclic heteroatoms, at least three of which are nitrogen atoms;
Ink composition.
(48)
48. The composition of item 47, wherein the organic group comprises tetrazolyl.
(49)
The organic group is

48. The composition according to item 47, wherein
(50)
The modified pigment is yellow pigment 1, 74, 155, 180, 185, 213, 218, 220, or 221, red pigment 122, 202, 254, or 269, blue pigment 15, 16, or 60, or purple pigment 19. 48. The composition according to item 47, comprising:
(51)
Pigments,
An organic group bonded to the pigment, and an organic group containing a 5-membered aromatic heterocyclic ring,
The composition wherein the 5-membered aromatic heterocycle contains 4 endocyclic heteroatoms, at least 3 of which are nitrogen atoms.
(52)
52. An article comprising the composition of item 51, wherein the article is an inkjet printer, coating, paint, toner, color filter, or electrophoretic display.

Claims (6)

Pigments,
A composition comprising an organic group bonded to the pigment,
The organic group is

A composition. The pigment includes pigment yellow 1, 74, 155, 180, 185 , 213, 218, 220, or 221, pigment red 122, 202, 254, or 269, pigment blue 15, 16, or 60, or pigment violet 19. including composition of claim 1. Liquid vehicle,
A composition according to claim 1 or 2 , and
An ink composition comprising: Pigments,
An organic group bonded to the pigment,
The organic group is

A composition. The pigment includes pigment yellow 1, 74, 155, 180, 185 , 213, 218, 220, or 221, pigment red 122, 202, 254, or 269, pigment blue 15, 16, or 60, or pigment violet 19. 5. A composition according to claim 4 comprising. Liquid vehicle,
A composition according to claim 4 or 5 , and
An ink composition comprising: